Thiazole derivatives

ABSTRACT

Certain N-[(heterocyclic)aminocarbonyl]thiazolesulfonamides, such as N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-4-thiazolesulfonamide, are useful as herbicides and/or plant growth regulants.

This is a continuation of application Ser. No. 609,695, filed May 14,1984 which is a continuation in part of application Ser. No. 479,363filed Apr. 4, 1983 now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to novelN-[(heterocyclic)aminocarbonyl]thiazolesulfonamides where theheterocycle is pyrimidine or thiazine, to herbicidal compositionscontaining them and to methods of using them to control the growth ofundesired vegetation.

New compounds effective for controlling the growth of undesiredvegetation are in constant demand. In the most common situation, suchcompounds are sought to selectively control the growth of weeds inuseful crops such as cotton, rice, corn, wheat and soybeans, to name afew. Unchecked weed growth in such crops can cause significant losses,reducing profit to the farmer and increasing costs to the consumer. Inother situations, herbicides are desired which will control all plantgrowth. Examples of areas in which complete control of all vegetation isdesired are areas around fuel storage tanks, ammunition depots andindustrial storage areas. There are many products commercially availablefor these purposes, but the search continues for products which are moreeffective, less costly and environmentally safe.

A number of different types ofN-[(heterocyclic)aminocarbonyl]arylsulfonamides are know as herbicides.Two of the first patents to issue on such compounds are U.S. Pat. Nos.4,169,719 and 4,127,405, issued on Oct. 2, 1979 and Nov. 28, 1978,respectively. These patents disclose compounds of the general formula##STR1## where W can be O or S,

Z can be N or CH, and

R is optionally substituted benzene, optionally substituted thiophene,optionally substituted furan or naphthalene.

Later publications have disclosed similar compounds where R₁ is athiophene or pyrrole. See, for example, European Patent Applications81302461.9, published Dec. 9, 1981, 82301500.3, published Nov. 17, 1982,80304287.8, published June 10, 1981, and 81301874.4, published Nov. 4,1981. Nowhere in the art is there a disclosure ofN-[(heterocyclic)aminocarbonyl]thiazolesulfonamides or any indicationthat such novel compounds would be useful as herbicides.

SUMMARY OF THE INVENTION

It has now been found that the novel compounds of Formula I possessherbicidal and/or plant growth regulant utility.

    QSO.sub.2 NHCONHA                                          I

where

Q is ##STR2## R is H, C₁ -C₃ alkyl or CH₃ C(O)NH; R₁ is H, C₁ -C₃ alkyl,C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, or C₁ -C₃ alkoxycarbonyl;

R₂ is H, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃alkoxycarbonyl, NO₂, Cl, Br or CF₃ ;

R₃ is H, Cl or CH₃ ;

R₄ is H, Cl or CH₃ ;

A is ##STR3## X is CH₃, C₂ H₅, OCH₃, OCF₂ H, OC₂ H₅ or CH₂ OCH₃ ;

Y is CH₃, OCH₃, OCF₂ H or cyclopropyl; and

Z is CH or N;

provided that (i) R₃ and R₄ are simultaneously Cl, and (ii) when eitherX or Y is OCF₂ H, then Z is CH; and agriculturally suitable saltsthereof.

This invention therefore relates to novel compounds of Formula I, toherbicidal compositions containing them, and to methods of using them tocontrol the growth of undesired vegetation.

Preferred for reasons of their high herbicidal activity, plant growthregulant activity and/or favorable ease of synthesis are the followinggroups of compounds:

(1) Compounds of Formula I where Z is CH.

(2) Compounds of Formula I where Z is CH and, when Q is Q-3, then R₄ isH.

(3) Compounds of Formula I where Z is CH and Q is Q-1 or Q-2.

(4) Compounds of Formula I where Z is CH and Q is Q-1, R is H or CH₃,and R₁ is H, CH₃, C₁ -C₂ alkoxy or C₁ -C₂ alkoxycarbonyl.

The following compounds are specifically preferred for reasons of theirhigh herbicidal activity, plant growth regulant activity and/orfavorable ease of synthesis:

N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-4-thiazolesulfonamide,m.p. 196°-200° (d);

N-[(4,6-dimethoxyprimidin-2-yl)aminocarbonyl]-4-thiazolesulfonamide,m.p. 201°-203° C.; and

5-ethoxy-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methyl-4-thiazolesulfonamide.

DETAILED DESCRIPTION Synthesis

The compounds of this invention where Q and A are as previously definedbut R is other than CH₃ CONH, may be prepared, as shown in Equation 1,by reaction of an appropriately substituted sulfonyl isocyanate ofFormula II with the appropriate heterocyclic amine of Formula III.##STR4##

The reaction of Equation 1 is generally carried out by adding a solutionof the sulfonyl isocyanate II in an inert solvent, such as methylenechloride or acetonitrile, to a solution or suspension of theheterocyclic amine III in the same solvent. The mixture is stirred fromabout one to twenty-four hours at temperatures from ambient to thereflux temperature of the solvent. In some cases, the reaction isexothermic and the compounds of Formula I crystallize from the reactionmixture. When the compounds of Formula I are soluble in the reactionmedium, they can be isolated by evaporation of the solvent andtrituration with a suitable solvent such as 1-chlorobutane or hexane.

Sulfonyl isocyanates of Formula II, where Q is as previously defined andR is other than CH₃ CONH, can be prepared, as shown in Equation 2, byreaction of sulfonamides of Formula IV with phosgene in the presence ofan alkyl isocyanate, such as butyl isocyanate, in an inert solvent, suchas xylene or chlorobenzene, according to the procedure of H. Ulrich andA. A. Y. Sayigh, "New Methods of Preparative Organic Chemistry", Vol.VI, p. 223-241, Academic Press, New York and London, W. Foerst, Ed.##STR5##

Alternatively, the reaction shown in Equation 2 can be carried out inthe presence of a catalytic amount of a tertiary amine, such astriethylamine or diaza[2.2.2]bicyclooctane, by the procedure describedin European Patent Application No. 80301848.0, published Jan. 7, 1981.

Alternatively, many compounds of Formula I, where Q and A are aspreviously defined, but R₁ and R₂ are other than C₁ -C₃ alkoxycarbonyl,may be prepared by the method described in Equation 3, namely, byreaction of a sulfonamide of Formula IV, where Q is as previouslydefined but R₁ and R₂ are other than C₁ -C₃ alkoxycarbonyl, with aheterocyclic carbamate of Formula V in the presence of at least onemolar equivalent of trimethylaluminum. ##STR6##

The reaction of Equation 4 is generally carried out in an inert solvent,such as methylene chloride or toluene, under an inert atmosphere, attemperatures from ambient up to the reflux temperature of the solventfor about 6-96 hours. The product can be isolated by addition of dilutehydrochloric acid to the cooled reaction mixture followed by separationof the organic phase, drying of the solution and evaporation of thesolvent. The product can be purified by trituration with, orcrystallization from, solvents such as 1-chlorobutane, hexane, ethanolor similar solvents.

Another procedure for the preparation of many compounds of thisinvention is by the reaction of a carbamate of Formula VI, where Q is aspreviously defined, with a heterocyclic amine III by methods analogousto the procedure described in European Patent Application 81810281.6(Publication Number 44,807), published July 3, 1981, as shown inEquation 4. ##STR7##

The compounds of Formula I of this invention also can be prepared, asshown in Equation 5, by contacting a sulfonamide of Formula IV, where Qis as previously defined, with a phenylcarbamate of Formula VII, where Ais as previously defined, in the presence of a molecular equivalent of1,5-diazabicyclo[5.4.0]undec-5-ene (DBU). The reaction of Equation 5 isgenerally carried out in an inert, water-miscible solvent, such asacetonitrile, dioxane or tetrahydrofuran, about ambient temperature forabout 0.5-6 hours. The product can be isolated by dilution of thereaction medium with water, acidification, followed by purification bymethods similar to those previously discussed. The carbamates of FormulaVII may be prepared by the methods, or modifications thereof known tothose skilled in the art, described in South African Patent Application825,045, filed July 15, 1982. ##STR8##

Sulfonamides of Formula IV can be prepared by amination of thecorresponding sulfonyl chlorides of Formula VIII by methods well knownin the art. The intermediate sulfonyl chlorides of Formula VIII can beprepared by one of the methods shown in Equation 6. ##STR9##

In Equations 6A and 6B, a solution or a suspension of a benzyl sulfideof Formula IX or a thiol of Formula X in aqueous acetic acid is treatedwith at least three molar equivalents of chlorine at temperatures ofabout 0° to 15°. The sulfonyl chloride of Formula VIII can be isolatedby dilution of the reaction mixture with water, followed by eitherfiltration or extraction with an organic solvent such as ether,methylene chloride or 1-chlorobutane.

In Equation 6C, a bromide of Formula XI is treated with one molarequivalent of n-butyl lithium, in solvents such as ether,tetrahydrofuran or dimethoxyethane, at temperatures of about -78° to-20°. The intermediate lithioheterocycle is added to an excess ofsulfuryl chloride in a solvent such as hexane or ether at temperaturesof about -20° to 0°. The sulfonyl chloride of Formula VIII can beisolated by addition of water to the reaction mixture, separation of theorganic solution, and evaporation of the solvents.

In Equation 6D, a heterocycle of Formula XII is treated with an excessof chlorosulfonic acid at temperatures of about ambient ot the boilingpoint of chlorosulfonic for periods of from several hours to severaldays. The sulfonyl chlorides of Formula VIII can be isolated by pouringthe reaction mixture into ice water, and either filtering the product orextracting it into an organic solvent.

In Equation 6E, a heterocyclic amine of Formula XIII is diazotized withsodium nitrite in a mixture of water, concentrated hydrochloric acid andacetic acid at temperatures from about -5° to 10°. The resultingdiazonium salt is added to a mixture of sulfur dioxide, cuprous orcupric chloride, concentrated hydrochloric acid and acetic acid, and thereaction mixture is stirred at temperatures from about 0° to ambient.The sulfonyl chloride of Formula VIII can be isolated by diluting thereaction mixture with water and either filtration or extraction with anorganic solvent.

The synthesis of the heterocyclic amines of Formula III has beenreviewed in "The Chemistry of Heterocyclic Compounds", a seriespublished by Interscience Publishers. 2-Aminopyrimidines are describedby D. J. Brown in "The Pyrimidines" in Vol. XVI of the series;2-aminotriazines are described by E. M. Smolin and L. Rapoport in"s-Triazines and Derivatives", in Vol. XIII of the series, both of theteachings of which are herein incorporated by reference. Compounds ofFormula III where X or Y is OCF₂ H can be prepared by the methodsdescribed in South African Patent Application 825,045.

Compounds of Formula III where Y is cyclopropyl can be prepared by themethods described in South African Patent Application 837,434.

Agriculturally suitable salts of compounds of Formula I are also usefulherbicides and can be prepared in a number of ways known to the art. Forexample, metal salts can be made by treating compounds of Formula I witha solution of alkali or alkaline earth metal salt having a sufficientlybasic anion (e.g., hydroxide, alkoxide, carbonate or hydride).Quaternary amine salts can be made by similar techniques.

Salts of compounds of Formula I can also be prepared by exchange of onecation for another. Cationic exchange can be effected by directtreatment of an aqueous solution of a salt of a compound of Formula I(e.g., alkali metal or quaternary amine salt) with a solution containingthe cation to be exchanged. This method is most effective when thedesired salt containing the exchanged cation is insoluble in water,e.g., a copper salt, and can be separated by filtration.

Exchange may also be effected by passing an aqueous solution of a saltof a compound of Formula I (e.g., an alkali metal or quaternary aminesalt) through a column packed with a cation exchange resin containingthe cation to be exchanged. In this method, the cation of the resin isexchanged for that of the original salt and the desired product iseluted from the column. This method is particularly useful when thedesired slat is water-soluble, e.g., a potassium, sodium or calciumsalt.

Acid addition salts, useful in this invention, can be obtained byreacting a compound of Formula I or II with a suitable acid, e.g.,p-toluenesulfonic acid, trichloroacetic acid or the like.

The compounds of this invention are further illustrated by the followingexamples, wherein temperatures are given in degrees centigrade and partsare by weight unless otherwise indicated.

EXAMPLE 1 4-Chloro-2-thiazolesulfonamide (IV; Q═Q-3, R₃ ═Cl)

A. Benzylmercaptan (24.8 g) was added dropwise to a solution of 10.8 gof sodium methoxide in 100 ml ethanol. After stirring 15 minutes, theehtanolic solution of sodium benzylmercaptide was added dropwise to asolution of 30.8 g 2,4-dichlorothiazole [prepared by the method of P.Reynaud et al., Bull. Soc. Chim. France, 1735 (1962)], resulting in atemperature increase of 28° to 48°. When the exotherm subsided, thesuspension was refluxed 1 hour, then the solvent was evaporated. Coldwater (300 ml) was added to the oily residue, and the aqueous mixturewas extracted with methylene chloride. The organic solution was washedwith water, followed by saturated brine, then dried over magnesiumsulfate, filtered and the solvent evaporated to give 43.8 g of4-chloro-2-phenylmethylthiothiazole as a brown oil.

B. A mixture of 43.8 g of 4-chloro-2-phenylthiothiazole, 225 ml aceticacid and 25 ml water was cooled to 4° and 29 ml of liquid chlorine wasadded dropwise while maintaining the temperature below 7°. When theaddition of chlorine was complete, the light yellow solution was stirred15 minutes at 0° prior to being poured into 1200 ml ice-water. Theaqueous mixture was extracted with ether; the organic solution waswashed with water, then dried over magnesium sulfate, filtered, and thesolvent evaporated. The residual yellow oil was dissolved in 200 ml oftetrahydrofuran, and 50 ml of ammonium hydroxide was added dropwise at25°-30°. The brown reaction mixture was stirred 1 hour at ambienttemperature. The reaction mixture was concentrated, diluted with 200 mlwater and acidified with acetic acid. The aqueous mixture was extractedwith methylene chloride. The organic solution was washed with water,dried over magnesium sulfate, filtered, and the solvent evaporated.Trituration of the resulting oily solid with 300 ml hexane, filtrationand washing with hexane gave 7.7 g of the title compound, m.p.137°-141.5°.

NMR (CDCl₃ /DMSO-d₆): δ 7.5 (s, 1H, 5-CH) and 7.7 (broad s, 2H, SO₂NH₂). IR: 3.06 and 3.28μ (SO₂ NH₂).

EXAMPLE 2N-[(4,6-Dimethoxypyrimidin-2-yl)aminocarbonyl]-4-chloro-2-thiazolesulfonamide(I; Q═Q-3, R₃ ═Cl, R₄ ═H, Z═CH, X═Y═OCH₃)

To a suspension of 1.6 g of 4-chloro-2-thiazolesulfonamide in 100 mlmethylene chloride under a nitrogen atmosphere, 4.4 ml of a 2.0Msolution of trimethylaluminum in toluene was added slowly via a syringe.The reaction mixture was stirred 10 minutes; 1.9 g of methylN-(4,6-dimethoxypyrimidin-2-yl)carbamate was added, and the reactionmixture refluxed for 18 hours. The reaction mixture was cooled to 0°,and 55 ml of 5% hydrochloric acid was added dropwise giving a flocculantsolid. The reaction mixture was extracted with 100 ml of ethyl acetate.The organic solution was washed with brine, dried over magnesiumsulfate, filtered and the solvent evaporated. The resulting tan solidwas slurried in 1-chlorobutane, collected, washed with hexane and driedgiving 1.25 g of the title compound as a white solid, m.p. 182°-183°(d).IR: 2.98 and 3.25μ(NH), 5.80μ (C═O).

NMR (CDCl₃ /DMSO-d₆): δ 3.90 (s, 6H, OCH₃), 5.9 (s, 1H, pyrimidine CH),7.95 (s, 1H, thiazole CH) and 11.2 (s, 1H, NH).

Calcd. for C₁₀ H₁₀ ClN₅ O₅ S₂ : C-31.62, H-2.66, N-18.43. Found: C-31.8,H-2.7, N:18.5 C-31.8, H-2.7, N-18.4.

EXAMPLE 3 4-Thiazolesulfonamide (IV; Q═Q-1, R═R₁ ═H)

A. Benzylmercaptan (24.8 g) was added slowly to a solution of 10.8 g ofsodium methoxide in 100 ml ethanol. After 10 minutes, the reactionmixture was heated to 65° C. and a solution of 23.8 g of4-chlorothiazole [prepared by the method of P. Reynaud et al., Bull.Soc. Chim. France, 1735 (1962)] in 25 ml ethanol was added dropwise.When addition was complete, the reaction mixture was refluxed 36 hours.The reaction mixture was cooled, and the bulk of the solvent evaporated.Cold water (300 ml) was added to the residue, and the aqueous mixturewas extracted with 200 ml ether followed by 200 ml methylene chloride.The combined organic solution was washed with brine, dried overmagnesium sulfate, filtered and the solvent evaporated. Distillation ofthe resulting yellow oil gave 15.6 g of 4-(phenylmethylthio)thiazole, bp122-134 (0.6 mm).

B. A mixture of 15.6 g of 4-(phenylmethylthio)thiazole in 75 ml aceticand 25 ml water was cooled to ˜5° and 12.0 ml of liquid chlorine wasadded dropwise at ˜5°. When the addition was complete, the yellowsolution was stirred 20 minutes at 0°, then poured into 500 ml icewater. The aqueous mixture was extracted with methylene chloride. Theorganic solution was washed twice with water, dried over magnesiumsulfate, filtered, and the solvent evaporated to give a yellow oil thatpartially crystallized on cooling. The crude sulfonyl chloride wasdissolved in 100 ml of tetrahydrofuran, and 12.0 ml of ammoniumhydroxide added dropwise at 5°-10°. The resulting brown suspension wasallowed to warm to ambient temperature, then concentrated to an oilysolid. Addition of 200 ml water and 100 ml methylene chloride to theoily solid gave a solid at the interface. The solid was collected,washed with water followed by hexane and dried giving 3.8 g of the titlecompound as a brown solid, m.p. 142°-146.5°. IR: 3.1 and 3.2μ (SO₂ NH₂).

NMR (CDCl₃ /DMSO-d₆): δ 7.15 (broad s, 2H, SO₂ NH₂), 8.1 (d, 1H, CH) and8.6 (d, 1H, CH).

EXAMPLE 4N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-4-thiazolesulfonamide(I; Q═Q-1, R═R₁ ═H, Z═CH, X═OCH₃, Y═CH₃)

By using the procedure described in Example 2, the reaction of 0.98 g of4-thiazolesulfonamide with 1.3 g of methylN-(4-methoxy-6-methylpyrimidin-2-yl)carbamate in the presence of 3.3 mlof a 2.0M solution of trimethylaluminum in toluene, there was obtained0.7 g of the title compound as an off-white solid, m.p. 196°-200° (d).IR: 5.89μ (C═O).

NMR (CDCl₃ /DMSO-d₆): δ 2.48 (s, 3H, CH₃), 3.90 (s, 3H, OCH₃), 6.45 (s,1H, pyrimidine CH), 8.67 (d, 1H, thiazole CH), 9.26 (d, 1H, thiazoleCH), 10.5 (s, 1H, NH) and 13.2 (s, 1H, NH).

EXAMPLE 5 5-Ethoxy-2-methyl-4-thiazolesulfonamide (IV; Q═Q-1, R═CH₃, R₁═OC₂ H₅)

A solution of 11.1 g of 4-bromo-5-ethoxy-2-methylthiazole [prepared bythe method of D. S. Tarbell et al., J. Amer. Chem. Soc., 72, 3138 (1950)in 50 ml ether was cooled to -60°, and 35.9 ml of a 1.7M solution ofn-butyl lithium in hexane was added dropwise while maintaining thetemperature below -45°. The resulting heavy yellow-brown suspension wasdiluted with an additional 25 ml ether and stirred 20 minutes at atemperature of -50° to -30°. The ethereal suspension of thelithiothiazole was added via syringe to a solution of 8.0 ml sulfurylchloride in 50 ml hexane, while maintaining the temperature between -30°and -20°. After the suspension was stirred 15 minutes at -30°, it wasallowed to warm to -5° and stirred 3.5 hours. The reaction mixture waspoured into 500 ml ice-water. The two-phase suspension was extractedtwice with ether. The combined organic solution was washed with waterand brine, then dried over magneisum sulfate, filtered, and the solventevaporated. The resulting oily solid was dissolved in 150 ml oftetrahydrofuran; the solution was cooled to 0°, and 6.7 ml of ammoniumhydroxide added dropwise. The brown suspension was allowed to warm toambient and stirred 3 hours. The solvent was evaporated, and theresidual black oil partitioned between methylene chloride and water. Theorganic solution was washed with water followed by brine, then stirred0.5 hour with magnesium sulfate and charcoal. The mixture was filteredthrough Celite@ and the solvent was evaporated. Trituration of theresulting brown oily solid with 1-chlorobutane gave 4.2 g of the titlecompound as a tan solid, m.p. 118°-120°. IR: 3.05 and 3.15μ (SO₂ NH₂).

NMR (CDCl₃ /DMSO-d₆): δ 1.25 (t, 3H, CH₃), 2.60 (s, 3H, CH₃), 4.22 (q,2H, OCH₂) and 6.10 (broad s, 2H, SO₂ NH₂).

EXAMPLE 65-Ethoxy-N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-methyl-4-thiazolesulfonamide(I; Q═Q-1, R═CH₃, R₁ ═OC₂ H₅, Z═CH, X═Y═OCH₃)

By employing the procedure described in Example 2, the reaction of 1.33g of 5-ethoxy-2-methyl-4-thiazolesulfonamide with 1.4 g of methylN-(4,6-dimethoxypyrimidin-2-yl)carbamate in the presence of 3.3 ml of a2.0M solution of trimethylaluminum, there was obtained 1.2 g of thetitle compound, m.p. 140°-143°. IR: 1710 cm⁻¹ (C═O).

NMR (CDCl₃): δ 1.5 (t, 3H, CH₃), 2.6 (s, 3H, CH₃), 3.95 (s, 6H, OCH₃),4.3 (q, 2H, OCH₂), 5.8 (s, 1H, pyrimidine CH₃), 7.5 (broad s, 1H, NH)and 13.0 (s, 0.67H, NH).

EXAMPLE 7 Methyl 5-(aminosulfonyl)-4-thiazolecarboxylate (IV; Q═Q-2,R═H, R₂ ═CO₂ CH₃)

A. A solution of 31.3 g of potassium t-butoxide in 280 ml oftetrahydrofuran was cooled to -50° and a solution of 27.7 g of methylisocyanoacetate in 230 ml of tetrahydrofuran was addd dropwise at -50°to -40°. The resulting brown suspension was stirred 15 minutes thencooled to -78°, then a solution of 16.8 ml of carbon disulfide in 225 mltetrahydrofuran was added dropwise while maintaining the temperaturebelow -50°. The pinkish-brown thick suspension was allowed to warm to-15° to 10° over 15 to 20 minutes. To the reaction mixture, a solutionof 33.3 ml of benzyl bromide in 140 ml tetrahydrofuran was addeddropwise at -15° to -5°. The reaction mixture was stirred at ambienttemperature for 30 minutes, refluxed for 20 minutes, then cooled and thebulk of the solvent evaporated. To the oily residue, 1000 ml ice-waterwas added. After several minutes, the product solidified. The tan solidwas collected, washed twice with water, followed by hexane and driedgiving 68.8 g of methyl 5-(phenylmethylthio)-4-thiazolecarboxylate, m.p.90°-92°.

B. A solution of 39.8 g of methyl5-(phenylmethylthio)-4-thiazolecarboxylate in 225 ml acetic acid and 25ml water was cooled to 3°, and 23.9 ml of liquid chlorine was addeddropwise below 10°. The yellow-brown solution was stirred 45 minutes at5°-10° before being poured into 1200 ml of ice-water to give a yellowoil which partially solidified on standing. The crude reaction productwas collected, washed with water, then four times with hexane and driedto give 29.4 g of methyl 5-(chlorosulfonyl)-4-thiazolecarboxylate, m.p.94°-97.5°.

C. A solution of 28.9 g of methyl5-(chlorosulfonyl)-4-thiazolecarboxylate in 150 ml tetrahydrofuran wascooled to 0° and 6.6 ml of liquid ammonia was added dropwise at 0°-10°.The suspension was allowed to warm to ambient temperature and stirred 1hour. The reaction mixture was filtered, the ammonium chloride washedwith tetrahydrofuran, and the solvent evaporated from the filtrate. Theresidual solid was slurried in hexane, collected and dried to give 25.0g of the title compound, m.p. 138°-140°. IR: 3.01 and 3.1μ (SO₂ NH₂) and5.8μ (C═O).

NMR (CDCl₃ /DMSO-d₆): δ 4.0 (s, 3H, OCH₃), 7.2 (broad s, 2H, SO₂ NH₂)and 9.0 (s, 1H, thiazole CH).

EXAMPLE 8 5-Methoxycarbonyl-4-thiazolesulfonyl isocyanate (II; Q═Q₁, R₁═CO₂ CH₃, R═H)

A mixture of 11.1 g of 5-(aminosulfonyl)-4-thiazolecarboxylate, 5.6 mlof butyl isocyanate and 0.17 g of diaza[2.2.2]bicyclooctane in 150 mlxylene was heated to reflux. Phosgene (4.2 ml) was added dropwise insmall portions to the reaction mixture, while maintaining thetemperature above 130°. When the last 0.5 ml of phosgene was added, thereaction temperature dropped to 124°. The reaction mixture refluxed 1hour, then the dry-ice condenser replaced with a water condenser, andthe mixture refluxed 30 minutes under a slow stream of nitrogen. Thereaction mixture cooled, filtered twice under nitrogen, and the solventevaporated from the filtrate to give the title sulfonyl isocyanate asthick yellow oil. IR: 4.45μ (SO₂ NCO).

The crude sulfonyl isocyanate was dissolved in 50 ml of methylenechloride for reactions with amino heterocycles.

EXAMPLE 9 Methyl5-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)aminosulfonyl]-4-thiazolecarboxylate(I; Q═Q-1; R₁ ═CO₂ CH₃, R═H, Z═CH, X═Y═OCH₃)

To a stirred suspension of 0.78 g of 4,6-dimethoxy-2-pyrimidinamine anda crystal of diaza[2.2.2]bicyclooctane in 5 ml of methylene chloride wasadded 11 ml of the methylene chloride solution prepared in Example 8.After the addition, a clear solution developed; a precipitate beganforming after approximately 30 minutes. The suspension was stirredovernight at ambient temperature. The solid was collected, washed with1-chlorobutane and dried giving 1.2 g of the title compound, m.p.172°-174° (d). IR: 1721 and 1790 cm⁻¹ (2×C═O).

NMR (CDCl₃ /DMSO-d₆): δ 3.97 (s, 3H, OCH₃), 4.02 (s, 6H, OCH₃), 5.8 (s,1H, pyrimidine CH), 9.1 (s, 1H, thiazole CH), 10.0 (broad s, 1H, NH) and13.1 (broad s, 1H, NH).

EXAMPLE 10 Ethyl 4-(aminosulfonyl)-2-methyl-5-thiazole carboxylate (IV;Q═Q-1, R═CH₃, R₁ ═CO₂ C₂ H₅)

A. A 5.05 g portion of 50% sodium hydride in mineral oil was washed withhexane and suspended in 100 ml of dimethylformamide. To this suspension,a solution of 19.57 g ethyl 4-hydroxy-2-methyl-5-thiazolecarboxylate in100 ml of dimethylformamide was added dropwise resulting in theformation of a heavy yellow gel. The reaction mixture was diluted with75 ml dimethylformamide and stirred for 30 minutes. A solution of 14.23g of dimethylthiocarbamyl chloride in 50 ml dimethylformamide was addeddropwise to the thick slurry, then the reaction mixture was heated at85°-95° for 45 minutes. The resulting brown suspension was cooled andpoured into a cold solution of 5.7 g sodium hydroxide in 1200 ml water.The aqueous mixture was extracted once with benzene and twice withether. The combined organic extracts were washed twice with waterfollowed by brine, then dried over magnesium sulfate, filtered and thesolvent evaporated giving an oil that partially crystallized. The crudereaction product was slurried in hexane, collected and dried giving 13.1g of ethyl4-[(dimethylamino)thioxomethyloxy]-2-methyl-5-thiazolecarboxylate, m.p.87°-90°.

B. A 12.3 g sample of the compound of Part A was heated at 170°-195°under a nitrogen atmosphere for 1.5 hour. The dark reaction mixture wascooled and dissolved in methylene chloride. The solvent was evaporatedto give a black oil which crystallized on scratching. Recrystallizationfrom hexane-ethyl acetate gave 9.2 g of ethyl4-[(dimethylamino)carbonylthio]-2-methyl-5-thiazolecarboxylate, m.p.84.5°-85.5°.

C. A 21.5 g sample of the compound prepared as in Part B was added to asolution of 2.7 g of sodium in 200 ml ethanol, and the reaction mixturestirred overnight at ambient temperature. The tan suspension wasconcentrated, the residue was dissolved in 500 ml water and the aqueoussolution acidified with cold, dilute hydrochloric acid. The aqueousmixture was extracted with methylene chloride; the organic solution wasdried over magnesium sulate, filtered and the solvent evaporated. Coldwater (200 ml) was added to the oily solid; the resulting solid wascollected, washed with water and dried giving 13.4 g of ethyl4-mercapto-2-methyl-5-thiazolecarboxylate, m.p. 62°-66°.

D. A solution of 14.4 g of the compound, prepared as in Part B, in amixture of 80 ml of acetic acid and 20 ml water was cooled to 0°, and11.3 ml of liquid chlorine was added dropwise at 0°-8°. The yellow-brownsolution was stirred 30 minutes at approximately 5°, then poured into500 ml water. The aqueous mixture was extracted twice with ether; theorganic solution was washed twice with water, dried over magnesiumsulfate, filtered and the solvent evaporated to give an oil. The crudesulfonyl chloride was dissolved in 100 ml tetrahydrofuran and thesolution cooled to 5°. Ammonium hydroxide (10.4 ml) was added dropwise;the reaction mixture had a pH <7. More ammonium hydroxide (4.4 ml) wasadded; the reaction mixture was allowed to warm to ambient temperatureand stirred 2 hours. The solvent was evaporated and 300 ml cold waterwas added to the residual oily solid. The resulting solid was collected,washed with water and dried giving 8.1 g of the title sulfonamide, m.p.129°-131.5°. IR: 3380 and 3225 cm⁻¹ (SO₂ NH₂), 1705 cm⁻¹ (C═O).

EXAMPLE 11 5-Ethoxycarbonyl-2-methyl-4-thiazolesulfonyl isocyanate (II;Q═Q-1, R═CH₃, R₁ ═CO₂ C₂ H₅)

A mixture of 7.5 g of the sulfonamide prepared in Example 9, 3.4 mlbutyl isocyanate, and a few crystals of diaza[2.2.2]bicyclooctane in 85ml xylene was heated to 136° and 2.3 ml of phosgene was added dropwise.The reaction temperature had dropped to 126° when addition of phosgenewas complete. The reaction mixture was refluxed 30 minutes; the dry-icecondenser replaced with a water condenser, and the mixture refluxed anadditional 30 minutes under a slow stream of nitrogen. The reactionmixture was cooled and filtered under nitrogen. Evaporation of thesolvent gave the title sulfonyl isocyanate as a yellow-brown oil. IR:2240 cm⁻¹ (SO₂ NCO) and 1760 cm⁻¹ (C═O).

The crude isocyanate was dissolved in 25 ml of methylene for reactionwith heterocyclic amines.

EXAMPLE 12 Ethyl4-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]-2-methyl-5-thiazolecarboxylate(I; Q═Q-2, R═CH₃, R₂ ═CO₂ C₂ H₅, Z═N, X═OCH₃, Y═CH₃)

A 7 ml portion of the methylene chloride solution of the sulfonylisocyanate, prepared in Example 10, was added to a stirred suspension of0.35 g of 4-methoxy-6-methyl-1,3,5-triazin-2-amine and a crystal ofdiaza[2.2.2]bicyclooctane in methylene chloride. The reaction mixturewas stirred overnight. The clear solution was concentrated to ayellow-brown oil. On lengthy trituration with ether, a solid wasobtained which was collected, washed with ether and dried to give 0.48 gof the title compound, m.p. 126°-130°. IR: 1725 and 1720 cm⁻¹ (2×C═O).

NMR (CDCl₃): δ 1.35 (t, 3H, CH₃), 2.6 (s, 3H, CH₃), 2.75 (s, 3H, CH₃),4.15 (s, 3H, OCH₃), 4.4 (q, 2H, OCH₂), 8.2 (broad s, 1H, NH) and 12.6(broad s, 1H, NH).

By the methods described in Examples 1-12, or modifications thereof, thecompounds of Tables I-III may be prepared.

                  TABLE I                                                         ______________________________________                                         ##STR10##                                                                    R     R.sub.1   X         Y      Z     m.p.(°C.)                       ______________________________________                                        H     H         OCH.sub.3 OCH.sub.3                                                                            CH    201-203°                        H     H         CH.sub.3  CH.sub.3                                                                             CH                                           H     H         CH.sub.3  OCH.sub.3                                                                            N                                            H     H         OCH.sub.3 OCH.sub.3                                                                            N                                            H     H         CH.sub.3  CH.sub.3                                                                             N                                            H     H         OC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             CH                                           H     H         CH.sub.2 OCH.sub.3                                                                      OCH.sub.3                                                                            CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        CH.sub.3  OCH.sub.3                                                                            CH    157-160°                        CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        CH.sub.3  CH.sub.3                                                                             CH    175-178°                        CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCH.sub.3 OCH.sub.3                                                                            CH    140-143°                        CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        CH.sub.3  OCH.sub.3                                                                            N                                            CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        CH.sub.3  CH.sub. 3                                                                            N                                            CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCH.sub.3 OCH.sub.3                                                                            N                                            H     OCH.sub.3 OCH.sub.3 OCH.sub.3                                                                            CH                                           H     OCH.sub.3 CH.sub.3  CH.sub.3                                                                             CH                                           H     OCH.sub.3 OC.sub.2 H.sub.5                                                                        OCH.sub.3                                                                            CH                                           H     OCH.sub.3 OCH.sub.3 OCH.sub.3                                                                            CH                                           H     OCH.sub.3 OCH.sub.3 CH.sub.3                                                                             N                                            H     OCH.sub.3 OCH.sub.3 CH.sub.3                                                                             N                                            H     OCH.sub.3 CH.sub.2 OCH.sub.3                                                                      OCH.sub.3                                                                            N                                            H     OC.sub.3 H.sub.7                                                                        OCH.sub.3 OCH.sub.3                                                                            CH                                           H     CH.sub.3  CH.sub.3  OCH.sub.3                                                                            N                                            H     C.sub.2 H.sub.5                                                                         CH.sub.3  CH.sub.3                                                                             CH                                           H     C.sub.3 H.sub.7                                                                         OCH.sub.3 OCH.sub.3                                                                            CH                                           CH.sub.3                                                                            SCH.sub.3 CH.sub.3  OCH.sub.3                                                                            CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCF.sub.2 H                                                                             CH.sub.3                                                                             CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCF.sub.2 H                                                                             CH.sub.3 O                                                                           CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCF.sub.2 H                                                                             OCF.sub.2 H                                                                          CH                                           CH.sub.3                                                                            SC.sub.2 H.sub.5                                                                        OCH.sub.3 OCH.sub.3                                                                            N                                            CH.sub.3                                                                            SC.sub.3 H.sub.7                                                                        CH.sub.3  OCH.sub.3                                                                            N                                            CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.3  CH.sub.3                                                                             CH    150-153°                        CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.3  OCH.sub.3                                                                            CH    87-97°                          CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                OCH.sub.3 OCH.sub.3                                                                            CH    121-123°                        CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.3  OCH.sub.3                                                                            N     126-130°                        CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                OCH.sub.3 OCH.sub.3                                                                            N     140-145°                        CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                CH.sub.2 OCH.sub.3                                                                      OCH.sub.3                                                                            N                                            CH.sub.3                                                                            CO.sub.2 C.sub.2 H.sub.5                                                                OC.sub.2 H.sub.5                                                                        CH.sub.3                                                                             N                                            H     CO.sub.2 CH.sub.3                                                                       CH.sub.3  CH.sub.3                                                                             CH                                           H     CO.sub.2 CH.sub.3                                                                       CH.sub.3  OCH.sub.3                                                                            CH                                           H     CO.sub.2 CH.sub.3                                                                       OCH.sub.3 OCH.sub.3                                                                            CH                                           H     CO.sub.2 CH.sub.3                                                                       OCH.sub.3 CH.sub.3                                                                             N                                            H     CO.sub.2 CH.sub.3                                                                       OCH.sub.3 OCH.sub.3                                                                            N                                            H     CO.sub.2 C.sub.3 H.sub.7                                                                OCH.sub.3 OCH.sub.3                                                                            CH                                           C.sub.2 H.sub.5                                                                     H         CH.sub.3  OCH.sub.3                                                                            N                                            C.sub.3 H.sub.7                                                                     SCH.sub.3 CH.sub.3  OCH.sub.3                                                                            CH                                           CH.sub.3                                                                            OCH.sub.3 OCF.sub.2 H                                                                             CH.sub.3                                                                             CH                                           CH.sub.3                                                                            OCH.sub.3 C.sub.2 H.sub.5                                                                         OCH.sub.3                                                                            CH                                           H     H         C.sub.2 H.sub.5                                                                         OCH.sub.3                                                                            N                                            H     H         C.sub.2 H.sub.5                                                                         OCH.sub.3                                                                            CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        C.sub.2 H.sub.5                                                                         OCF.sub.2 H                                                                          CH                                           H     H         OCH.sub.3                                                                                ##STR11##                                                                           N                                            H     H         CH.sub.3                                                                                 ##STR12##                                                                           CH                                           CH.sub.3                                                                            OC.sub.2 H.sub.5                                                                        OCH.sub.3                                                                                ##STR13##                                                                           N                                            ______________________________________                                    

                  TABLE II                                                        ______________________________________                                         ##STR14##                                                                    R       R.sub.2  X        Y       Z    m.p.(°C.)                       ______________________________________                                        CH.sub.3 CONH                                                                         CH.sub.3 CH.sub.3 CH.sub.3                                                                              CH                                          CH.sub.3 CONH                                                                         CH.sub.3 CH.sub.3 OCH.sub.3                                                                             CH                                          CH.sub.3 CONH                                                                         CH.sub.3 OCH.sub.3                                                                              OCH.sub.3                                                                             CH   191-                                                                          195° (d)                        CH.sub.3 CONH                                                                         CH.sub.3 CH.sub.3 CH.sub.2 OCH.sub.3                                                                    CH                                          CH.sub.3 CONH                                                                         CH.sub.3 CH.sub.3 CH.sub.3                                                                              N                                           CH.sub.3 CONH                                                                         CH.sub.3 OCH.sub.3                                                                              OCH.sub.3                                                                             N                                           CH.sub.3 CONH                                                                         CH.sub.3 OCH.sub.3                                                                              OC.sub.2 H.sub.5                                                                      N                                           CH.sub.3 CONH                                                                         CH.sub.3 CH.sub.3 OCH.sub.3                                                                             N                                           H       C.sub.2 H.sub.5                                                                        OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          H       C.sub.3 H.sub.7                                                                        CH.sub.3 OCH.sub.3                                                                             N                                           CH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          CH.sub.3                                                                              OC.sub.2 H.sub.5                                                                       CH.sub.3 OCH.sub.3                                                                             CH                                          CH.sub.3                                                                              OC.sub.3 H.sub.7                                                                       CH.sub.3 OCH.sub.3                                                                             CH                                          C.sub.2 H.sub.5                                                                       SCH.sub.3                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                             N                                           C.sub.3 H.sub.7                                                                       H        CH.sub.3 OCH.sub.3                                                                             CH                                          H       CO.sub.2 CH.sub.3                                                                      CH.sub.3 CH.sub.3                                                                              CH   174-                                                                          175° (d)                        H       CO.sub.2 CH.sub.3                                                                      OCH.sub.3                                                                              CH.sub.3                                                                              CH   179-                                                                          180° (d)                        H       CO.sub.2 CH.sub.3                                                                      OCH.sub.3                                                                              OCH.sub.3                                                                             CH   172-                                                                          174° (d)                        H       CO.sub.2 CH.sub.3                                                                      CH.sub.3 OCH.sub.3                                                                             N    166-                                                                          169° (d)                        H       CO.sub.2 CH.sub.3                                                                      OCH.sub.3                                                                              OCH.sub.3                                                                             N    177-                                                                          178° (d)                        H       CO.sub.2 C.sub.2 H.sub.5                                                               OCH.sub.3                                                                              CH.sub.3                                                                              CH                                          H       CO.sub.2 C.sub.3 H.sub.7                                                               CH.sub.3 OCH.sub.3                                                                             CH                                          CH.sub.3 CONH                                                                         CH.sub.3 OCF.sub.2 H                                                                            CH.sub.3                                                                              CH                                          H       H        CH.sub.3 OCH.sub.3                                                                             N                                           H       H        OCH.sub.3                                                                              OCH.sub.3                                                                             N                                           H       H        CH.sub.3 OCH.sub.3                                                                             CH                                          H       H        OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          CH.sub.3 CONH                                                                         CF.sub.3 CH.sub.3 OCH.sub.3                                                                             CH                                          CH.sub.3 CONH                                                                         NO.sub.2 OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          CH.sub.2 CONH                                                                         Br       OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          CH.sub.3 CONH                                                                         Cl       OCH.sub.3                                                                              OCH.sub.3                                                                             CH                                          CH.sub.3                                                                              CO.sub.2 CH.sub.3                                                                      OCH.sub.3                                                                               ##STR15##                                                                            N                                           CH.sub.3                                                                              CO.sub.2 CH.sub.3                                                                      CH.sub.3                                                                                ##STR16##                                                                            CH                                          ______________________________________                                    

                  TABLE III                                                       ______________________________________                                         ##STR17##                                                                    R.sub.3                                                                             R.sub.4 X         Y       Z     m.p.(°C.)                        ______________________________________                                        Cl    H       CH.sub.3  OCH.sub.3                                                                             CH    182-183° (d)                     Cl    H       OCH.sub.3 OCH.sub.3                                                                             CH    80-84° (d)                       Cl    H       CH.sub.3  CH.sub.3                                                                              CH                                            Cl    H       CH.sub.3  OCH.sub.3                                                                             N                                             Cl    H       CH.sub.3  CH.sub.3                                                                              N                                             Cl    H       OCH.sub.3 OCH.sub.3                                                                             N                                             H     H       OCH.sub.3 CH.sub.3                                                                              CH                                            H     CH.sub.3                                                                              CH.sub.3  OCH.sub.3                                                                             N                                             CH.sub.3                                                                            CH.sub.3                                                                              OCH.sub.3 OCH.sub.3                                                                             CH                                            CH.sub.3                                                                            H       CH.sub.3  OCH.sub.3                                                                             CH                                            H     Cl      OCH.sub.3 OCH.sub.3                                                                             CH                                            Cl    H       OCF.sub.2 H                                                                             CH.sub.3                                                                              CH                                            H     H       C.sub.2 H.sub.5                                                                         OCH.sub.3                                                                             CH                                            H     H       OCH.sub.3                                                                                ##STR18##                                                                            N                                             ______________________________________                                    

Formulations

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient(s) and at least one of (a) about 0.1% to 20%surfactant(s) and (b) about 1% to 99.9% solid or liquid inertdiluent(s). More specifically, they will contain these ingredients inthe following approximate proportions:

                  TABLE IV                                                        ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., N.Y., 1964, listsurfactants and recommended uses. All formulations can contain minoramounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley and Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 13

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                      80%                                               4-thiazolesulfonamide                                                         sodium alkylnaphthalenesulfonate                                                                           2%                                               sodium ligninsulfonate       2%                                               synthetic amorphous silica   3%                                               kaolinite                   13%                                               ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 14

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          50%                                                4-thiazolesulfonamide                                                         sodium alkylnaphthalenesulfonate                                                                          2%                                                low viscosity methyl cellulose                                                                            2%                                                diatomaceous earth         46%                                                ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 15

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable Powder of Example 14                                                                         5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 16

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                      25%                                               4-thiazolesulfonamide                                                         anhydrous sodium sulfate    10%                                               crude calcium ligninsulfonate                                                                              5%                                               sodium alkylnaphthalenesulfonate                                                                           1%                                               calcium/magnesium bentonite 59%                                               ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 17

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                           0.1%                                              4-thiazolesulfonamide                                                         attapulgite granules       99.9%                                              (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 18

    ______________________________________                                        Granule                                                                       ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          80%                                                4-thiazolesulfonamide                                                         wetting agent               1%                                                crude ligninsulfonate salt (containing                                                                   10%                                                5-20% of the natural sugars)                                                  attapulgite clay            9%                                                ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 19

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       1%                                               4-thiazolesulfonamide                                                         N,N-dimethylformamide        9%                                               attapulgite granules        90%                                               (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 20

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                           40%                                               4-thiazolesulfonamide                                                         polyacrylic acid thickener 0.3%                                               dodecylphenol polyethylene glycol ether                                                                  0.5%                                               disodium phosphate           1%                                               monosodium phosphate       0.5%                                               polyvinyl alcohol          1.0%                                               water                      56.7%                                              ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 21

    ______________________________________                                        Solution                                                                      ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       5%                                               4-thiazolesulfonamide, sodium salt                                            water                       95%                                               ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 22

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                           99%                                               4-thiazolesulfonamide                                                         silica aerogel             0.5%                                               synthetic amorphous silica 0.5%                                               ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 23

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                       90%                                              4-thiazolesulfonamide                                                         dioctyl sodium sulfosuccinate                                                                             0.1%                                              synthetic fine silica       9.9%                                              ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 24

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          40%                                                4-thiazolesulfonamide                                                         sodium ligninsulfonate     20%                                                montmorillonite clay       40%                                                ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 25

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                      35%                                               4-thiazolesulfonamide                                                         blend of polyalcohol carboxylic                                                                            6%                                               esters and oil soluble petroleum                                              sulfonates                                                                    xylene                      59%                                               ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

EXAMPLE 26

    ______________________________________                                        Dust                                                                          ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          10%                                                4-thiazolesulfonamide                                                         attapulgite                10%                                                pyrophyllite               80%                                                ______________________________________                                    

The active ingredient is blended with attapulgite and then passedthrough a hammer-mill to produce particles substantially all below 200microns. The ground concentrate is then blended with powderedpyrophyllite until homogeneous.

EXAMPLE 27

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N-[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                      25%                                               4-thiazolesulfonamide                                                         polyoxyethylene sorbitol hexaoleate                                                                        5%                                               highly aliphatic hydrocarbon oil                                                                          70%                                               ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 28

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          20%                                                4-thiazolesulfonamide                                                         sodium alkylnaphthalenesulfonate                                                                          4%                                                sodium ligninsulfonate      4%                                                low viscosity methyl cellulose                                                                            3%                                                attapulgite                69%                                                ______________________________________                                    

The ingredient are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

Utility

Test results indicate that the compounds of the present invention areactive herbicides. They should have utility for broad-spectrum pre-and/or post-emergence weed control in areas where complete control ofall vegetation is desired, such as around fuel storage tanks, ammunitiondepots, industrial storage areas, parking lots, drive-in theaters,around billboards, highway and railroad structures. Alternatively, manyof the subject compounds should be useful for the selective pre- orpost-emergence weed control in crops, such as wheat and barley.

The rate of application for the compounds of the invention aredetermined by a number of factors, including their use as selective orgeneral herbicides, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foilage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.125 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for selective weed control orfor situations where only short-term persistence is required. Thecompounds are applied to the locus of the plants to be controlled, i.e.,to the soil in which seeds are planted for pre-emergence control or tothe plants themselves for post-emergence control.

The compounds of the invention may be used in combination with any othercommercial herbicide examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether , carbamate andbipyridylium types.

The herbicidal properties of the subject compounds were discovered in anumber of greenhouse tests. The test procedures and results follow.

Test A

Seeds of crabgrass (Digitaria sp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), sicklepod (Cassia obtusifolia),morningglory (Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn,soybean, sugar beet, rice, wheat and purple nutsedge (Cyperus rotundus)tubers were planted and treated pre-emergence with the test chemicalsdissolved in a non-phytotoxic solvent. At the same time, these crop andweed species, along with cotton and bush bean, were treated with asoil/foliage application. At the time of treatment, the plants ranged inheight from 2 to 18 cm. Treated plants and controls were maintained in agreenhouse for sixteen days, after which all species were compared tocontrols and visually rated for response to treatment. The ratings,summarized in Table A, are based on a numerical scale extending from0=no injury, to 10=complete kill. The accompanying descriptive symbolshave the following meanings:

C=chlorosis/necrosis;

E=emergence inhibition;

G=growth retardation;

H=formative effect;

P=terminal bud kill;

S=albinism;

X=axillary stimulation; and

6Y=abscised buds or flowers. ##STR19##

    TABLE A      Cmpd. 1 Cmpd. 2 Cmpd. 3 Cmpd. 4 Compound 5 Compound 6 Compound 7     Compound 8 Rate kg/ha 0.05 0.05 0.05 0.05 0.05 0.4 2 0.05 0.4 0.05 0.4     0.05 0.4 2       POST-EMERGENCE Bush bean 4C,9G,6Y 2C,5G,6Y 5S,9G,6Y 4C,5G,6Y 0 2G --     6C,9G,6Y 9C 3C,5G,6Y 9C 0 0 -- Cotton 4C,9G 3C,9G 4C,5H,9G 5C,9G -- --     4C,9G -- -- -- -- -- -- 0 Morningglory 4C,9G 3C,7G 0 1C,3G 0 2C,2H 3C,6H     4C,8H 7C 2C 2C,9H 0 0 1C Cocklebur 5C,9G 9C 10C 10C 0 3C,7H 5C,9H 3C,8G     9C 3C,9H 10C 0 0 2C,5H Sicklepod 3C,9G 4C,9G 1C 2H 0 1C 3C,3H 1C 2C 2C     1C,2G 0 2C 1C Nutsedge 9G 9G 0 0 0 0 5G 0 2C 2C,3G 3C,8G 0 0 0 Crabgrass     2C,6G 2C,5G 0 0 0 0 5G 2C 2C,7G 2C 2C,5G 0 0 0 Barnyardgrass 2C,9H 4C,8H     0 0 0 3H 5C,9H 3C,8H 5C,9H 2C,3H 2C,9H 0 1H 5C,9H Wild Oats 2C,8G 2C,9G     0 0 0 0 0 0 0 0 0 0 0 0 Wheat 1C,8G 2C,9G 0 0 0 0 2G 0 2G 0 0 0 0 2C,6G     Corn 4U,9G 2U,9G 3H 1H 0 2C,2H 2C,6H 2C,5H 2C,9H 2C,5H 2C,9G 0 2H 3U,9G     Soybean 9C 9C 3H 5C,9G 0 1H 2C,8G 2C,3H 3C,8G 2C,5H 5C,9G 0 0 1C Rice     5C,9G 4C,9G 0 0 0 0 4C,9G 3G 2C,8G 3G 2C,8G 0 0 5C,9G Sorghum 9G 2C,9G     2G 0 0 2G 3C,8H 1C,3G 3C,7G 2C,4G 3C,9H 0 0 3C,8H Sugar beet -- -- -- --     -- -- 5C,9G -- -- -- -- -- -- 1C,2H PRE-EMERGENCE Morningglory 9G 8G 6G     5G 0 0 9G 8G 8H 3G 9H 0 0 0 Cocklebur 8H 8H 8H 8H 0 0 9H -- 9H 8H 9H 0 0     2G Sicklepod 9G 9G 5G 7G 0 0 7G 2G 1C 2C 1C 0 0 -- Nutsedge 3G 10E 0 5G     0 0 0 0 0 0 2C,8G 0 0 0 Crabgrass 3C,7G 5G 1C 0 0 0 0 0 2C,5G 2G 2C,5G 0     0 0 Barnyardgrass 3C,7G 3C,6G 2C 2C 0 0 3G 3H 5C,9H 2G 4C,9H 0 0 2G Wild     Oats 3C,8H 6G 0 0 0 0 0 0 1C 0 0 0 0 0 Wheat 9H 2C,8G 0 0 0 0 2G 0 7G 0     0 0 0 0 Corn 3C,9G 2C,8G 2C,6H 2C,6G 0 0 2C,5G 1C,3G 3C,9H 2C 2C,7G 0 0     2C,3G Soybean 8H 1H 1C 2C 0 0 2C 1C,1H 3C,5H 1C 3C,6H 0 0 0 Rice 9H 9H     2G 2C 0 2C,5G 9H 2C,7G 10E 2C,6G 4C,9H -- 0 4C,9H Sorghum 3C,9H 2C,9G 0     2G 0 0 4C,8H 2G 3C,9H 2G 3C,7H 0 0 3C,6G Sugar beet -- -- -- -- -- --     4C,9G -- -- -- -- -- -- 0 Cotton -- -- -- -- -- -- 6G -- -- -- -- -- --     0  Compound 9 Compound 10 Cmpd. 11 Cmpd. 12 Cmpd. 13 Compound 14 Cmpd.     15 Cmpd. 16 Cmpd. 17 Cmpd. 18 Rate kg/ha 0.05 0.4 2 0.05 0.4 0.05 0.05     0.05 0.05 0.4 0.05 0.05 0.05 0.05       POST EMERGENCE Bush bean 0 1C -- 4C,9G,6Y -- 5C,9G,6Y 9C 4C,9G,6Y     5C,8G,6Y -- 3S,8G,6Y 9C 5C,9G,6Y 3C,9G,6Y Cotton -- -- 0 4C,5G 3C,9G     4C,8G 4C,9H 2C,4G 2C 3C,5G 2C,3G 3C,9G 4C,8G 4C,8G Morningglory 0 0 3G     3C 3C,6G 4C,8G 4C,9H 2C,4H 2C 3C,5G 2C 5C,9G 5C,8G 3C,7H Cocklebur 0 0 0     3C,8H 5C,9G 9C 10C 2C 2C 3C,8H 2C 4C,9G 5C,9G 2C,8G Sicklepod 0 0 0 2C     3C,8G 3C,6H 5C,9H 2C 2C 3C,5H 2C 6C,9G 6C,9G 3C,5H Nutsedge 0 0 0 0     3C,9G 2C,7G 3C,8G 4G 0 1C,4G 1C 2C,8G 9G 9G Crabgrass 0 0 1C,4G 0 1C,3G     1C 4G 0 0 1C,3G 1C,4G 4C,9H 4C,8G 3C,3G Barnyardgrass 0 0 3C,9H 1C 3C,8H     2C,7H 9C 1C 1C,2H 2C,6H 3C,6G 4C,9H 5C,9G 1C Wild Oats 0 0 0 0 1C,9G     1C,4G 5G 0 0 4G 0 3C,9G 2C,7G 0 Wheat 0 0 2G 0 3C,9G 8G,5X 7G 3G 0 3G 0     3C,9G 5C,9G 2G Corn 0 0 8G 2C 3C,9G 2C,9H 2U,9G 2C,8H 1C 1U,8G 1C,3G     2C,9G 5U,9C 9G,5I Soybean 0 0 0 1C,2G 6C,9G 5C,9G 9C 2C,4G 1C,2H 6C,9G     2C,8G 5C,9G 9C 3C,9G Rice 0 0 3C,8G 2C,6G 3C,8G 4C,9G 2C,9G 5C,9G 5C,9G     5C,9G 4C,8G 5C,9G 4C,9G 5C,9G Sorghum 0 0 1C,4H 3C,9H 3C,9G 4C,9H 3C,9G     2C,9G 1C,5G 3C,9H 4C,9G 5C,9G 3C,9G 9G,5I Sugar beet -- -- 0 3C,8H 5C,9G     3C,8H 10C 3C,7H 2C,5G 3C,8H -- -- -- -- PRE-EMERGENCE Morningglory 0 0 0 1     C 3C,9G 9G 9C 1C,2H 2C 9G 2G 9G 9G 2C,7H Cocklebur -- 0 0 6H 9H 9H 9H 5G     0 8G 0 8H 8H 2G Sicklepod 0 0 -- 1C,5G 2C,5G 9G,2C 9G 1C 1C 8G 1H 9G 9G     4G Nutsedge 0 0 0 0 2C,8G 7G 8G 0 0 0 0 6G 10E 0 Crabgrass 0 0 0 0 3G 0     1C 0 0 0 0 2C,8G 3C,6G 3G Barnyardgrass 0 0 2C 1C 2C 2C,6G 3C,8H 1C 0 2C     1C 6C,9H 3C,9H 2C Wild Oats 0 0 0 0 3C,8H 3G 2C,7G 2C 0 2C,8G 1H 4C,7G     2C,6H 4G Wheat 0 0 0 0 1C,7G 2C,9H 2C,9G 3C,8G 0 2C,8G 0 2C,9G 9G 1C,6G     Corn 0 0 2C,4G 2C 3C,9H 2C,9H 2C,9H 2C,6G 1C 3C,8H 2C,3G 3C,9G 4C,9G     2C,7G Soybean 0 0 0 0 3G 2C,5H 2C,6H 1C 1H 2C,2H 1C,1H 3C,9H 5H 2C,2H     Rice 0 0 3C,9H 2C 4C,9H 3C,8H 3C,9H 2C,9H 6H 10E 0 3C,9H 9H 9H Sorghum 0     0 3C,7G 2C,7G 4C,9H 3C,9H 3C,9H 4C,9H 2C,6G 4C,9H 3C,4G 9H 5C,9H 2C,9G     Sugar beet -- -- 0 1C,2G 9C 10E 10E 1C,1H 0 4C,8G -- -- -- -- Cotton --     -- -- -- 9C -- -- -- -- 6G -- -- -- --

Several compounds were tested according to the procedure described belowto further define their activity as pre-emergence herbicides.

Test B

Two plastic bulb pans were filled with fertilized and limed Woodstownsandy loam. One pan was planted with corn, sorghum, Kentucky bluegrassand several grass weeds. The other pan was planted with cotton, soybean,purple nutsedge (Cyperus rotundus), and several broadleaf weeds. Thefollowing grass and broadleaf weeds were planted: crabgrass (Digitariasanquinalis), barnyardgrass (Echinochloa crusgalli), wild oats (Avenafatua), johnsongrass (Sorghum halepense), dallisgrass (Paspalumdilatatum), giant foxtail (Setaria faberii), cheatgrass (Bromussecalinus), mustard (Brassica arvensis), cocklebur (Xanthiumpensylvanicum), moriningglory (Ipomoea hederacea), sicklepod (Cassiaobtusifolia), teaweed (Sida spinosa), velvetleaf (Abutilon theophrasti),and jimsonweed (Datura stramonium). A 12.5 cm diameter plastic pot wasalso filled with prepared soil and planted with rice and wheat. Another12.5 cm pot was planted with sugar beets. The above four containers weretreated pre-emergence with several test compounds within the scope ofthe invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data for severalcompounds are summarized in Table B. A number of other compounds werealso tested and all were shown to have activity as pre-emergencetreatments for the control of a number of species at rates as low as0.03 kg/ha. Several of the compounds were safe on wheat.

                  TABLE B                                                         ______________________________________                                        PRE-EMERGENCE ON                                                              WOODSTOWN SANDY LOAM                                                                     Compound 1  Compound 2                                             Rate kg/ha   0.03    0.12      0.03  0.12                                     ______________________________________                                        Crabgrass    0       0         4G    5G                                       Barnyardgrass                                                                              0       4G        2G    5G,3H                                    Sorghum      8G,5H   9G,9C     7G,5H 9G,9C                                    Wild Oats    3G      6G        0     5G                                       Johnsongrass 4G      4G        0     4G,3H                                    Dallisgrass  6G      9G        3G    3G                                       Giant foxtail                                                                              2G      2G        0     0                                        Ky. bluegrass                                                                              0       8G        0     6G                                       Cheatgrass   7G      9G        6G    8G                                       Sugar beets  7G      8G        5G    7G                                       Corn         3G,3C   6G,3C     2G    4G,3C                                    Mustard      9G,9C   9G,9C     8G    9G                                       Cocklebur    2G      6G        0     6G                                       Nutsedge     10C     10C       5G    10C                                      Cotton       4G      6G        4G    6G                                       Morningglory 5G,3C   6G,3H     0     5G,5H                                    Sicklepod    7G      7G        0     7G                                       Teaweed      --      --        --    --                                       Velvetleaf   10C     10C       8G    9G,9C                                    Jimsonweed   4G      8G,8C     0     8G,8C                                    Soybean      3G,3C   7G,5C     2G,2C 5G,3C                                    Rice         9G,9C   10C       8G    10C                                      Wheat        0       2G        0     0                                        ______________________________________                                    

Several compounds were tested according to the following procedure tobetter define their post-emergence utility.

Test C

The test chemicals, dissolved in a non-phytotoxic solvent, were appliedin an overall spray to the foliage and surrounding soil of selectedplant species. One day after treatment, plants were observed for rapidburn injury. Approximately fourteen days after treatment, all specieswere visually compared to untreated controls and rated for response totreatment. The rating system was as described previously for Test A. Thedata are presented in Table C.

All plant species were seeded in Woodstown sandy loam soil and grown ina greenhouse. The following species were grown in soil contained inplastic pots (25 cm diameter by 13 cm deep): soybeans, cotton, alfalfa,corn, rice, wheat, sorghum, velvetleaf (Abutilon theophrasti), sesbania(Sesbania exaltata), sicklepod (Cassia obtusifolia), morningglory(Ipomoea hederacea), jimsonweed (Datura stramonium), cocklebur (Xanthiumpensylvanicum), crabgrass (Digitaria sp.), nutsedge (Cyperus rotundus),barnyardgrass (Echinochloa crusgalli), giant foxtail (Setaria faberii)and wild oats (Avena fatua). The following species were grown in soil ina paper cut (12 cm diameter by 13 cm deep): sunflower, sugar beets, andrape. All plants were sprayed approximately 14 days after planting.Additional plant species, such as johnsongrass and field bindweed, aresometimes added to this standard test in order to evaluate unusualselectivity.

Several of the compounds tested by this procedure are useful for thepost-emergence control of weeds in wheat.

                  TABLE C                                                         ______________________________________                                        Over-the-Top Soil/Foliage Treatment                                           Rate kg/ha  0.06         0.015   0.004                                        ______________________________________                                                  Compound 1                                                          Soybeans    9C           6C,8G   3C,4G                                        Velvetleaf  9C           9G      8G                                           Sesbania    9G           6C,7G   3G                                           Sicklepod   8G           7G      3G                                           Cotton      8G           7G      3G                                           Morningglory                                                                              9G           7G      3G                                           Alfalfa     9C           8C      4G                                           Jimsonweed  9G           6G      4G                                           Cocklebur   9G           5G      0                                            Sunflower   9G           7C      4G                                           Rape        10C          9C      5G                                           Sugar beets 10C          9C      8G                                           Corn        7G,5C        6G,2C   3H,4G                                        Crabgrass   0            0       0                                            Rice        3G,6C        2G,4C   1G                                           Nutsedge    3G           2C      0                                            Barnyardgrass                                                                             3G           2G      0                                            Wheat       3G           1G      0                                            Giant foxtail                                                                             4G           1G      0                                            Wild Oats   7G,4C        2G      0                                            Sorghum     8G           8G      7G                                           Johnsongrass                                                                              4C,5G        3G      0                                            Field Bindweed                                                                            8G           8G      2G                                                     Compound 2                                                          Soybeans    10C          7G      2G                                           Velvetleaf  10C          9G      7G                                           Sesbania    10C          8G      5G                                           Sicklepod   10C          9G      5G                                           Cotton      9G           9G      9G                                           Morningglory                                                                              9G,5C        8G      0                                            Alfalfa     9G,5C        9G      9G                                           Jimsonweed  4G           0       0                                            Cocklebur   8G           --      3G                                           Sunflower   10P          10P     3G                                           Rape        10C          9G,5C   6G                                           Sugar beets 10C          10C     10C                                          Corn        8G           8G,2H   3G                                           Crabgrass   8G           0       0                                            Rice        7G           7G      2G                                           Nutsedge    8G           8G      0                                            Barnyardgrass                                                                             8G           5G      0                                            Wheat       2G           0       0                                            Giant foxtail                                                                             2G           2G      2G                                           Wild Oats   4G           4G      0                                            Sorghum     7G           7G      2G                                           Johnsongrass                                                                              7G           7G      2G                                           Field Bindweed                                                                            8G           9G      4G                                           ______________________________________                                    

The following test was performed to investigate the utility of compoundsof this invention as selective herbicides in wheat and barley.

Test D

Two plastic pans lined with polyethylene liners were filled withprepared Woodstown sandy loam soil. One pan was planted with seeds ofwheat (Triticum aestivum), barley (Hordeum vulgare), wild oats (Avenafatua), cheatgrass (Bromus secalinus), blackgrass (Alopecurusmyosuroides), annual bluegrass (Poa annua), green foxtail (Setariaviridis), Italian ryegrass (Lolium multiflorum) and rapeseed (Brassicanapus). The other pan was planted with seeds of Russian thistle (Salsolakali), cleavers (Galium aparine), speedwell (Veronica persica), kochia(Kochia scoparia), shepherd's purse (Capsella bursa-pastoris),Matricaria inodora, black nightshade (Solanum nigrum), wild buckwheat(Polygonum convolvulus) and sugar beets (Beta vulgaris). Other specieswhich sometimes are added to this test include downy brome (Bromustectorum), quackgrass (Agropyron repens), ripgut brome (Bromus rigidus),tansy mustard (Descuraina pinnata), tumble mustard (Sisymbriumaltissium) and yellow rocket (Barbarea vulgaris). The above two panswere treated pre-emergence. At the same time two pans in which the aboveplant species were already growing were treated post-emergence. Plantheight at the time of treatment ranged from 1-20 cm depending on plantspecies.

The compounds applied were diluted with a nonphytotoxic solvent andsprayed over-the-top of the pans. An untreated control and a solventalone control were included for comparison. All treatments weremaintained in the greenhouse for 19-22 days at which time the treatmentswere compared to the controls and the effects visually rated. Therecorded data for one of the compounds are presented in Table D. It canbe seen that Compound No. 2 has utility or pre- or post-emergence weedcontrol in wheat and barley.

                  TABLE D                                                         ______________________________________                                                   Compound 2                                                         Rate g/ha    4           15      60                                           ______________________________________                                        Pre-Emergence                                                                 wheat        0           0       1G                                           barley       0           0       0                                            wild oats    0           0       6G                                           downy brome  0           2G      9G                                           cheatgrass   0           2G      5G                                           blackgrass   0           0       6G                                           annual bluegrass                                                                           0           0       5G                                           green foxtail                                                                              0           0       3G                                           quackgrass   0           3G      6G                                           Italian ryegrass                                                                           0           2C,5G   7C,9G                                        ripgut brome 0           4G      8G                                           Russian thistle                                                                            0           0       0                                            tansy mustard                                                                              2C,9G       10C     10C                                          Galium aparine                                                                             --          --      --                                           tumble mustard                                                                             8G          2C,8G   10C                                          kochia       0           0       8G                                           shepherd's purse                                                                           2C,8G       10C     9C,9G                                        Matricaria inodora                                                                         8G          9G      8C,9G                                        black nightshade                                                                           0           2G      5G                                           yellow rocket                                                                              2G          2C,6G   9G                                           rapeseed     2G          2C,8G   2C,9G                                        wild buckwheat                                                                             0           2G      4G                                           Post-Emergence                                                                wheat        0           0       2G                                           barley       0           0       2G                                           wild oats    0           0       3G                                           downy brome  0           2G      4G                                           cheatgrass   0           2G      3G                                           blackgrass   0           3G      5G                                           annual bluegrass                                                                           3G          4G      5G                                           green foxtail                                                                              0           --      --                                           quackgrass   0           0       6G                                           Italian ryegrass                                                                           0           6G      1C,6G                                        ripgut brome 0           0       5G                                           Russian thistle                                                                            0           --      0                                            tansy mustard                                                                              7G          3C,8G   9C,9G                                        Galium aparine                                                                             3C,8G       8G      10C                                          tumble mustard                                                                             10C         9C,9G   10C                                          kochia       3G          5G      8G                                           shepherd's purse                                                                           6G          7C,8G   10C                                          Matricaria inodora                                                                         6G          3C,8G   9C,9G                                        black nightshade                                                                           5G          4G      4G                                           yellow rocket                                                                              5G          7G      7C,8G                                        rapeseed     7G          8G      5C,8G                                        wild buckwheat                                                                             5G          8G      3C,8G                                        ______________________________________                                    

What is claimed is:
 1. A compound of the formula:

    QSO.sub.2 NHCONHA

where Q is ##STR20## R is H, C₁ -C₃ alkyl or CH₃ C(O)NH; R₁ is H, C₁ -C₃alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio or C₁ -C₃ alkoxycarbonyl; R₂ isH, C₁ -C₃ alkyl, C₁ -C₃ alkoxy, C₁ -C₃ alkylthio, C₁ -C₃ alkoxycarbonyl,NO₂, Cl, Br or CF₃ ; R₃ is H, Cl or CH₃ ; R₄ is H, Cl or CH₃ ; A is##STR21## X is CH₃, OCH₃, OC₂ H₅ or CH₂ OCH₃ ; Y is CH₃, or OCH₃ ; and Zis N;provided that R₃ and R₄ are not simultaneously Cl, andagriculturally suitable salts thereof.
 2. A compound of claim 1 whereinX is CH₃, OCH₃, OC₂ H₅ or CH₂ OCH₃ ; and Y is CH₃ or OCH₃.
 3. A compoundof claim 1 where Q is ##STR22##
 4. A compound of claim 1 where Q is##STR23##
 5. An agricultural composition comprising an herbicidallyeffective amount of one or more compounds of claim 1 and at least one ofthe following: (a) a surfactant and (b) a solid or liquid diluent.
 6. Amethod for controlling the growth of undesired vegetation comprisingapplying to the locus of such vegetation an agriculturally effectiveamount of one or more compounds of claim
 1. 7. An agriculturalcomposition comprising an herbicidally effective amount of one or morecompounds of claim 2 and at least one of the following: (a) a surfactantand (b) a solid or liquid diluent.
 8. An agricultural compositioncomprising an herbicidally effective amount of one or more compounds ofclaim 3 and at least one of the following: (a) a surfactant and (b) asolid or liquid diluent.
 9. An agricultural composition comprising anherbicidally effective amount of one or more compounds of claim 4 and atleast one of the following: (a) a surfactant and (b) a solid or liquiddiluent.
 10. A method for controlling the growth of undesired vegetationcomprising applying to the locus of such vegetation an agriculturallyeffective amount of one or more compounds of claim
 2. 11. A method forcontrolling the growth of undesired vegetation comprising applying tothe locus of such vegetation an agriculturally effective amount of oneor more compounds of claim
 3. 12. A method for controlling the growth ofundesired vegetation comprising applying on the locus of such vegetationan agriculturally effective amount of one or more compounds of claim 4.